Stilbyl-acenaphthenotriazole



FIP8389 3,101,333 STILBYL-ACENAPHTHENOTRIAZOLE BRIGHTENERS Dennis ArthurWilliam Adams, Leeds, and Asim Kumar Sarkar, Adel, England, assignors toHickson & Welch Limited, Castleford, England, a British company NoDrawing. Filed Aug. 4, 1960, Ser. No. 47,399 Claims priority,application Great Britain Oct. 9, 1956 4 Claims. (Cl. 260-240) Thisinvention is concerned with improvements in or relating to opticalwhitening agents and is particularly concerned with certain newcompounds of use as optical whitening agents. This application is acontinuation-inpart of our application Serial No. 688,427, filed October7, 1957, and now abandoned.

Optical whitening agents have in recent years found extensive use in thetreatment of textiles particularly during washing and are designed tocounteract the yellow or off-white colour which white textiles,particularly cellulosic textiles, may possess, especially after repeatedwashing. Such optical whitening agents also tend to improve colouredtextiles as they impart a general brightness to them. They are alsowidely used to impartwhiteness to other cellulosic material,particularly paper.

Optical whitening agents in general absorb light in the ultra-violetrange of the spectrum and emit in the visible spectrum, usually in thebluish-green to bluish-violet. Thus, the fluorescence of such compoundsin white material tends to counteract any yellowing as, for example thatresulting upon repeated washing of a white cotton, linen or polyamidetextile. The compounds used as optical whitening agents must besubstantive to the material being treated, and must be substantiallystable when dyed on the material being treated.

In general best results are obtained with optical whitening agents whichgive a shade of fluorescence which is complementary to that of the agedfibre, so that the colours will cancel out each other. Since, ingeneral, the most common oll-white shade of textiles resulting fromaging or repeated washing is yellow, the most desirable opticalWhitening agent is one that fiuoresces blue.

It is also of importance that the optical whitening agent should not bedestroyed or removed by bleaching agents; that is, it should bebleach-fast. Thus, fluorescent optical whitening agents are generallyincorporated into soaps and synthetic detergents, which are marketed forhousehold use and articles washed therewith are often subjected tobleaching with various bleaching agents, for example sodiumhypocthlorite. It is therefore desirable that the optical whiteningagents already on the fibre or in the treating solution should beattected as little as possible by the action of any bleaching agentwhich may be present.

It is an object of the present invention to provide optical whiteningagents having improved properties in the foregoing respects.

We have now found that certain new compounds represented by the generalformula:

CH: IL,

and amine salts, can be used with advantage as optical whitening agentsin that they possess favourable properties from the point of view of theabove-mentioned desiderata for the ideal optical whitening agents.

Accordingly the invention comprises such compounds together withwater-soluble salts thereof in particular alkali metal, eg sodium orpotassium, ammonium and amine salts.

The term water soluble salts is used in the sense in which it iscommonly employed in the art relating to optical whitening agents thatis to mean those salts which have a sufiicient solubility in water tomake possible their application from aqueous media onto material beingtreated. As is known, optical whitening agents of the stilbyl-triazoletype have in general a comparatively low solubility in water, but it isusual to classify those compounds in this art which can be applied fromaqueous media as water-soluble. This is, in general, because opticalwhitening agents are normally applied at very low concentrations so thateven a compound which has a very low absolute solubility may well, forthe purpose of its use as an optical whitening agent, be classified aswatersoluble.

The compounds of the present invention show a good afiinity torcellulosic material and exhibit a blue fluorescence, giving to the fibrea particularly pleasant hue. They also have a good aflinity for variouspolyamide fibres. They show in general good resistance .to bleachingagents and have good build-up qualities; that isdue to well-balancedsubstantivity-on repeated treatments with a bath of the sameconcentration the whiteness of the fabric being treated continuallyincreases upto a maximum, which maximum does not in general causeunpleasant visible colour or hue, as is often the case. The amine saltsshow excellent substantivity to cellulosic fibres such as cotton underneutral conditions and thus are particularly suitable for application tosuch fibres from neutral treating solutions. The alkanolamine salts alsoshow a particularly good dispersibility.

The compounds according to the present invention can with advantage beincorporated in compositions normally used for the treatment oftextiles, for example detergents and soaps in solid or liquid form. Theymay also be incorporated in baths for the treatment of cellulosic orpolyamide materials during their production or for treatment of finishedtextile articles. In addition, the new compounds may also beincorporated in compositions for the treatment of paper and photographicpaper where high whiteness is necessary.

There is provided therefore according to a feature of the invention acomposition adapted for the treatment of textile material, in particularcellulosic and polyamide materials composing one or more compounds ofthe general [formula I above or water soluble, in particular alkalimetal, ammonium and amine salts thereof. The invention also includescellulosic and other textile materials when treated with the abovecompositions, in particular cotton or linen textiles, and nylon.

Preferred amine salts of the compounds of the general formula I includethose formed with primary, secondary and tertiary alkylamines andprimary, secondary and tertiary alkanolamines, in particular thoseformed with lower alkylamines (primary, secondary and tertiary) andthose formed with lower alkanolamines (primary, secondary and tertiary).Representative amines within these classes include the following:

n-P-ropanolamine Di-n-propanolamine Tri-n-propanolamine n-PropylamineDi-n-propylamine Tri-n-propylamine hili lilbi'l liUUltii 3 4Illustrative preferred new compounds according to the invention includethe following compounds together with CHE their alkali metal, ammonium,alkylamine and alkanolamine salts, CH2

2-(4"-styryl- 3 sulphophenyl)(acenaphtheno 6:7- 5 NH;4:5)-1:2:3-triazole.

2-(4"-(4"'-methoxy styryl) 3" sulphophenyl) (ace- I naphtheno-6' 7'-4 5-l :2 3-triazole. Y- Y 2-(4"-styryl-3-sulphophenyl)(3' sulphoacenaphtheno-6':7'-4:5)-l :2: 3-triazole. 10 Y2-(4"-styryl-3"-sulphophenyl) (5' chloro acenaph- 2:341riazo1e. where Yvhas the above stated meaning. The intermediate 2 (4- (4m chlorostyryl)sulphophenylxacenapb compound may if desired be isolated before beingcoutheno-6:7-4:5)-122:3-triazole. pled- 2 chlorostyryl sulphophenyl)(ace, The water soluble salts according to the invention may be preparedin general by the reaction of the parent 2 ,(4" (2'" 1 h 1)su1phopheny1)(ace acid with an appropriate base. In the case of thealkali 1 metal salts these may conveniently be prepared by using, Apartioulafly prefemsd new compound is as starting material, analkali-metal salt of the stilbene styryl sulphophenyl) (acenaphtheno';7' 4:5 sulphonic acid for diazotization and coupling with the1:2:3-triazole. aminoacenaphthene moiety, the stilbyl triazole product,In the above compounds the nomenclature adopted is after oxidation ofthe o-amino azo dye being then isolated based on the numbering shownbelow: in the form of its alkali metal salt. Alternatively one x x i N 56!" 5" 6" Ill X X SO 3 The new compounds of the general Formula Iaccordmay react the free acid with an alkali-metal hydroxide, ing to theinvention can conveniently be prepared by or carbonate thereby obtainingthe alkali metal salt. The oxidising an o-amino azo dye of Formula IIgiven below, 40 ammonium salt may be prepared in an analogous manandaccording to a further feature of the invention therener. fore there isprovided a process for the preparation of The amine salts canconveniently be prepared by direct the compounds of the general FormulaI above by reaction of the free acid with the amine for example byoxidising an o-amino azo dye of the general formula dissolving the acidin an excess of the amine, the reaction X X Y if desired being carriedout at an elevated temperature. I I CH: Isolation of the reactionproduct may be effected in any convenient manner.

OH: In order that the invention may be more fully under- X X SOSH stoodthat the following examples are given by way of illustration only:

H EXAMPLE 1 K 2-(4-Styryl-3"-Sulphoplzenyl) (Acenaphtheno-6:7'-

1 4:5 )-1 :2:3-Triaz0le (m A solution of 16.32 parts of the sodium saltof 4-amino- (where X and Y have the above-stated meanings).stilbenez-sulphonic acid P and Parts Of Mild oxidising agents are rferred f flecting h sodium nitrite in 150 parts water is indirectlydiazotized above reaction such as an alkali-metal hypochlorite, for atWith 20 Parts of Concentrated hydrochloric example sodium hypochlorite;cuprarnmoniurn sulphate The diaZO compound is isolated, Suspended in orcopper sulphate in the form of a soluble complex aqueous alcohol andmixed with a solution of 10.3 gins. ith pyridine as ll as thionyl h1 idd 1 h 1 of S-amino-acenaphthene hydrochloride in acidified aquehl id mayl be used. The oxidation is f bly ous alcohol. The acidity of themixture is controlled by fi t d t l t d t t the addition of sodiumacetate during coupling. When The o-amino azo dye above-mentioned may beprethe coupling is complete the o-amino azo dyestuil obtained pared inany convenient manner, such as, for example, 1s filtered at C by,diazotizing a compound f the f l The o-amino azo dyestufi is dissolvedin aqueous alcohol and refluxed with an excess of diethanolamine and 5copper sulphate (20 gms.). On completion of the oxidation the desiredproduct is obtained by acidification of the X CH=CH hot filtrate. Thecompound is slurried with aqueous alco- X so H hol, made alkaline andtreated with sodium hydrosulphite a for a few hours at l00 C. to removethe last traces (where X has the above-stated meaning), and coupling ofcoloured impurities. Finally the compound is crystalthe resultantdiazotized compound with a compound of lised from aqueous alcohol.

the formula:

5 The compound so obtained is a brownish yellow powder which in dilutesolution gives vivid blue fluorescence and when a piece of cotton iswashed in a detergent solution containing a small amount of thiscompound the material acquires a much whiter appearance than beforetreatment. The compound as the sodium salt has A max. 370 mu.

The compound may also be prepared as follows:

A solution of 16.32 pants of sodium salt of 4-aminostilbene-2-sulphonicacid (91% pure) and 3.45 parts of sodium nitrite in 150 parts of wateris indirectly diazotized at 8-10 C. with parts concentrated hydrochloricacid. The diazo compound is isolated, suspended in water and mixed witha solution of 10.3 parts of S-amino-acenaphthene hydrochloride in dilutehydrochloric acid. The acidity of the mixture is controlled by theaddition of sodium acetate during coupling. When the coupling iscompleted the o-amino azo dyestutf obtained is filtered off at 30 C.

The o-amino azo dyestuff is dissolved in butanol and refluxed with anexcess of ammonia and 20 parts of copper sulphate.

On completion of the oxidation the product is obtained by acidificationof the hot solution. The compound is recrystallised from aqueouspyridine. In the form of the sodium salt it has A max. 370 mp.

EXAMPLE 2 A solution of 16.68 parts of the sodium salt of4-methoxy-4-aminostilbene-2-sulphonic acid (98% pure) and 3.45 parts ofsodium nitrite in 150 parts of water is directly diazotized at 810 C.with 20 parts of concentrated hydrochloric acid. The diazo compound isisolated, suspended in water and mixed with a solution ofS-aminoacenaphthene hydrochloride in dilute hydrochloric acid. Theacidity of the mixture is controlled by the addition of sodium acetateduring coupling. When the coupling is complete the o-amino azo dyestufiobtained is filtered off at 2530 C. The o-amino azo dyestuff isdissolved in aqueous pyridine and refluxed with an excess of ammonia and20 parts of copper sulphate. On completion of the oxidation the productis obtained by acidification of the hot solution. The compound isrecrystallised from aqueous pyridine. In the form of the sodium salt ithas A max. 375 mp.

EXAMPLE 3 2-(4"-Styryl-3"-Sulphophenyl) (3-Sulphoacenaphthen0-6'.'7-4:5) :2 :3-Triaz0le A solution of 16.32 parts of the sodium saltof 4-aminostilbene-Z-sulphonic acid (91% pure) and 3.45 parts of sodiumnitrite in 150 parts of water is indirectly diazot-ized at 8-10 C. with20 parts concentrated hydrochloric acid. The diazo compound is isolated,suspended in water and mixed with a solution of 14.73 parts of sodiumsalt of 5-amino-acenaphthene-8-sulphonic acid in water. The acidity ofthe mixture is controlled by the addition of sodium acetate duringcoupling. When the coupling is complete the o-amino azo dyestufiobtained is filtered ofi at 2530 C.

The o-amino azo dyestufi is dissolved in water and refluxed with excessof ammonia and 20 parts of copper sulphate.

On completion of the oxidation the product is obtained by acidificationof the hot solution. The compound is recrystallised from aqueouspyridine. The sodium salt has A max. 370 mu.

EXAMPLE 4 2-(4"-Styryl-3"-Sulphophenyl) (5'-Chl0r0-Acenaphthen0-6':7-4:5 :2:3-Triaz0le A solution of 16.32 partsof the sodium salt of 4-arninostilbene-Z-sulphonic acid (91% pure) and3.45 parts of sodium nitrite in 150 parts of water is indirectly diazo-6 tized at 8-10 C. with 20 parts of concentrated hydrochloric acid. Thediazo compound is isolated, suspended in water and mixed with a solutionof 13.79 parts 6-- chloro-S-aminoacenaphthene hydrochloride in dilutehydrochloric acid. The acidity of the mixture is controlled by theaddition of sodium acetate during coupling. When the coupling iscompleted the o-amino azo dyestulf obtained is filtered ofl at 2530 C.

The o-amino azo dyestuif is dissolved in pyridine and refluxed with anexcess of ammonia and 20 parts of copper sulphate.

On completion of the oxidation the product is obtained by acidification0f the hot solution. The compound is recrystallised from aqueouspyridine. The sodium salt has A max. 372 mp.

EXAMPLE 5 2-(4'-Chl0r0styryl-3"-Sulphophenyl) (Acenaphtheno- 6':7 '-4 :5-1 :2 :3-Triazole A solution of 18.41 parts of the sodium salt of 4chloro 4 aminostilbene 2 sulphonic acid pure) and 3.45 parts of sodiumnitrite in parts water is indirectly diazotized at 810 C. with 20 partsconcentrated hydrochloric acid. The diazo compound is isolated,suspended in water and mixed with a solution of 10.3 parts ofS-aminoacenaphthene hydrochloride in dilute hydrochloric acid. Theacidity of the mixture is controlled by the addition of sodium acetateduring coupling. When the coupling is complete the o-arnino azo dyestuifobtained is filtered off at 2530 C.

The o-amino azo dyestuft is dissolved in pyridine and refluxed with anexcess of ammonia and 20 parts of copper sulphate. On completion of theoxidation the product is obtained by acidification of the hot solution.The compound is recrystallised from aqueous pyridine. The sodium salthas A max. 371 III/.4.

EXAMPLE 6 This is prepared as in Example 5 replacing 4-chloro-4-aminostilbene-2-sulphonic acid by2'-chloro-4-aminostilbene-Z-sulphonic acid. The sodium salt has A max.370 mu.

EXAMPLE 7 2-(4" (-2Sulph0styryl) -3"-Sulph0phenyl) (Acenaphthen0-6:7-4:5 -1 :2 :3-Triazole A solution of 28.1 parts of the sodium salt of4-aminostilbene-2:2-disulphonic acid (71% pure) and 3.45 parts of sodiumnitrite in 150 parts of water is indirectly diazotized at 8-10 C. with20 parts of concentrated hydrochloric acid. The diazo compound isisolated, suspended in water and mixed with a solution of 10.3 parts ofS-aminoacenaphthene hydrochloride in dilute acetic acid. The acidity ofthe mixture is controlled by the addition of sodium acetate duringcoupling. When the coupling is complete the o-amino azo dyestufiobtained is filtered off at 2530 C.

The o-amino azo dyestulf is dissolved in dilute sodium hydroxidesolution and refluxed with an excess of ammonia and 20 parts coppersulphate. On completion of the oxidation the product is obtained byacidification of the hot solution.

The compound is obtained by recrystallising from aqueous alcohol. Thesodium salt has A max. 370 m EXAMPLE 8 A piece of aged white poplin(slightly yellow) was washed with a detergent solution containing 0.05g. per litre of the compound obtained in Example 1. After rinsing anddrying the cloth showed a brilliant white appearance.

Example 1.

7 EXAMPLE 9 EXAMPLE l Monoethanolamine Salt 02-(4"-Styryl-3-Sulph0phenyl) (Acenaphthen0-6 :7'-4 -1 :2 :3-Triaz0legms. of 2 (4" styryl 3 sulphophenyl)(acephtheno-6:7-4:5)-1z2z3-triazole, are dissolved in 50 gms. ofmonoethanolamine by heating to 120. The solution is cooled and thenadded to 600 ccs. of water with stirring.

The precipitated monoethanolamine salt is filtered and washed with hotwater. The compound on drying has a decomposition point of 298 C.

EXAMPLE l1 Diethylamine Salt of 2-(4"-Styryl-3-Sulph0phenyl)(Acenaphthen0-6 :7 -4 :5 -1 :2 :3 -Triazole 10 gms. of 2 (4" styryl 3sulphophenyl) (acenaphtheno-6':7'-4:5)-1:2z3-triazole, are dissolved in100 gms. of diethylamine and then in 250 ccs. of 80% aqueous dioxan, inthe manner of Example 10.

The solution is cooled, diluted with water and filtered. The residue isre-slurried in 90% alcohol, filtered and Washed with hot water. Thediethylamine salt on drying has a decomposition point of 250. C.

EXAMPLE 12 Triethanolamine Salt of 2-(4"-Styryl-3-Sulph0phenyl)(Acenaphthen0-6':7-4:5 -1:2:3-Triaz0le 10 gms. of 2 (4" styryl 3sulphophenyl) (acenaphtheno-6:7'-4:5 )-1:2:3-triazole, are dissolved in100 gms. of triethanolamine and a little water by warming. The solutionis cooled, drowned in water and the precipitate filtered. Theprecipitate is re-crystallised from 95% alcohol. The decomposition pointof the triethanolamine salt is 200-203 C.

EXAMPLE l3 Morpholine Salt of 2-(4"-Styryl-3-Sulphophenyl)(Acenaphtheno-(i 7'4 :5 -1 :2 :3-Triaz0le '10 gms. of2-(4"-styryl-3-sulphophenyl) (acenaphtheno- 6':7-4:5)-1:2:3 triazole aredissolved in 200 gms. of morpholine and a little water by warming. Thesolution is drowned in water as before. The precipitate is filtered andre-slurried with hot 90% alcohol. The slurry is filtered and the soliddried in the usual manner. The decomposition point of morpholine salt is2936 C.

It will be appreciated that although only compounds in which the groupsX and Y are hydrogen, chloro, methoxy and sulphonic acid groups havebeen exemplified in the foregoing examples, the nature of these groupsis not restricted thereby. Thus, for example it will be clear to thoseskilled in the art that the groups X and Y can be other halogen or loweralkoxy groups or lower alkyl groups and need not necessarily berestricted to the groups specified in the examples. Other possibilitiesfor the groups X and Y will be further apparent to those skilled in theart.

and (2) a water-soluble salt of said compound selected from the groupconsistingof alkali metal, ammonium, lower alkylamine and loweralkanolamine salts.

3. A compound selected from the group consisting of (1) a compound ofthe formula C II:

' in which X, Y and Z are each halogen, a is an integer from 1 to 5, bis an integer from 1 to 4 and c is an integer from 1 to 2, at least oneof said integers being at least 2, and (2) a water-soluble salt of saidcompound selected from the group consisting of alkali metal, ammonium,lower alkylamine and lower alkanolamine salts.

4. A compound selected from the group consisting of (1) a compound ofthe formula in which X, Y and Z are each lower alkyl, a is an integerfrom 1 to 5, b is an integer from 1 to 4 and c is an integer from 1 to2, at least one of said integers being at least 2, and (2) awater-soluble salt of said compound selected from the group consistingof alkali metal, ammonium, lower alkylamine and lower alkanolaminesalts.

References Cited in the file of this patent UNITED STATES PATENTS2,784,183 Keller et al Mar. 5, 1957 2,784,184 Zweidler et a1. Mar. 5,1957 2,972,611 Zweidler et al. Feb. 21, 1961 OTHER REFERENCES Charrieret al.: Gazz. Chim. Ital., volume 55, pages 745 to 754 (1925).

Beilsteins Handbuch der Org. Chem, volume 26, 4th edition EII (SystemNo. 3812), pages 47-48 (1954).

1. 2 - (4" - STYRYL - 3" - SULPGOPHENYL) (ACENAPHTHENO6'':7''-4:5)-1:2:3-TRIAZOLE.
 2. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A COMPOUND OF THE FORMULA 